Method for producing renewable middle-distillate composition, use of the composition and fuel containing the same

ABSTRACT

The present invention provides a fuel comprising a renewable middle distillate composition obtainable by hydrodeoxygenation of a feedstock comprising levulinic acid dimers/oligomers and fractionated distillation. The renewable middle distillate composition contains less than 10.0 wt.-% aromatics.

TECHNICAL FIELD

The present invention relates to a method for producing a renewablemiddle-distillate hydrocarbon composition, use of the composition andfuel containing the composition. In particular, the present inventionrelates to hydrocarbon compositions obtained by hydrotreatment oflevulinic acid dimers/oligomers derived from renewable sources for theproduction of fuel or fuel components, to fuel containing thesehydrocarbon compositions and to the use of these hydrocarboncompositions as aviation fuel.

BACKGROUND ART

US 2012/0283493 A1 discloses various methods for treatment of fattyacids and lignocellulosic material including a hydrodeoxygenationtreatment.

WO 2006/067171 A1 discloses conversion of a reactant selected from alactone, a carboxylic acid having a γ-keto group or its ester to anon-cyclic saturated carboxylic acid or ester, wherein the non-cyclicsaturated esters can be used in diesel fuel.

EP 2 924 097 A2 discloses, a C—C-coupling reaction of levulinic acidwhich produces up to 35 wt.-% dimers as well as (higher) oligomers. Theproduct may be subjected to HDO treatment and then fractionated for usee.g. as diesel, aviation or gasoline fuel. The gasoline fraction maycontain less than 10 wt.-% aromatics The diesel fraction, which is amiddle distillate fraction, contains at least 30 wt.-% aromatics.

WO 2015/144994 A1 discloses thermal C—C-coupling of levulinic acid whichresults e.g. in dimers, followed by HDO and optional isomerization.Gasoline, aviation and diesel range fractions may be obtained byfractionation. WO 2015/144994 A1 states that isomerization results in areduction of cyclic compounds but remains silent regarding contents ofaromatics in middle distillate fractions.

DISCLOSURE OF THE INVENTION

The present invention relates to a method for producing a renewablemiddle-distillate hydrocarbon composition, use of the composition andfuel containing the composition. The composition is particularlysuitable as a component in aviation fuel/jet fuel, but may be used indiesel range fuel as well. In particular, the present invention relatesto compositions obtained by hydrotreatment of levulinic aciddimers/oligomers derived from renewable sources for the production offuel or fuel components, to fuel containing these compositions and tothe use of these compositions as aviation fuel.

Up to date, there are three ASTM-certified production paths forrenewable aviation fuel: Fischer-Tropsch synthesis, hydroprocessing ofesters and fatty acids (HEFA) and direct sugar to hydrocarbon (DSHC)conversion. According to a vision of the Ministry of Transport, andCommunication in Finland, 40% of currently used aviation fuels will bereplaced by biokerosine in 2050. This large amount requires alternativesources for the production of renewable aviation fuel, in particularhigh-quality fuel meeting highest demands.

Accordingly, the production of high-quality aviation fuel from renewablesources which are available in large amounts is still a problem to besolved. Further, the increasing use of bio-diesel poses the problem offinding suitable sources for the production of bio-diesel or bin-dieseladditives having desirable fuel characteristics.

These problems are solved by the, methods, the products and the use asdefined in the appended claims.

Specifically, the present invention provides middle-distillatecompositions which can be used as fuel components without furtherpurification due to their low content of undesired components,

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows BOCLE lubricity (mm) as a function of the content ofrenewable middle distillate composition of the present invention inblends with fossil fuel (Ex.3)

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a renewable middle-distillatecomposition usable as a component of aviation fuel or diesel fuel, whichis obtained by hydrotreatment of levulinic add dimers/oligomers whichare obtained from a renewable source.

Specifically, the present invention relates to a fuel comprising therenewable middle distillate composition, wherein the renewable middledistillate composition is obtainable by hydrodeoxygenation (orhydrotreatment) of a feedstock comprising levulinic aciddimers/oligomers, followed by fractionated distillation. Thefractionated distillation is carried out so as to obtain the middledistillate fraction from the, product obtained after hydrodeoxygenation.The renewable middle distillate composition contains less than 10.0wt.-% of aromatics, as determined in accordance with ASTM D2425.

The renewable middle distillate composition preferably contains at most9.5 wt.-%, at most 9.3 wt.-%, at most 9.0 wt.-%, at most 8.0 wt.-%, atmost 7.0 wt.-%, at most 6.0 wt.-%, at most 5.0 wt.-%, at most 4.0 wt.-%,or at most 3.0 wt.-% of aromatics, as determined in accordance with ASTMD2425.

The present inventors surprisingly found that a middle distillatefraction having very low aromatics content can be produced fromlevulinic acid dimers/oligomers. Low aromatics content is favourable inview of emissions and combustion characteristics.

Due to the use of the feedstock containing levulinic aciddimers/oligomers, the product distribution is narrow and the productproperties can be controlled in a well specified range. Furthermore, theresulting product (i.e. the middle distillate fraction) provides a verylow freezing point when used alone or in combination with conventionalfuel. Furthermore, the cloud point of diesel fuel is very low as wellwhen employing the middle distillate as an admixture. Thus, high-qualityfuel can be produced using lignocellulosic material as a renewablesource which is available in large amounts.

In the present invention, the levulinic acid may be employed in acidform or as a derivative selected from the group of esters of levulinicacid and/or lactones of levulinic add. Accordingly, the levulinic aciddimers/oligomers include all kinds of dimers/oligomers obtained fromlevulinic acid (free acid form) alone, levulinic acid esters alone,levulinic add lactones alone and mixed dimers/oligomers of these. In thepresent invention, the expression “containing levulinic aciddimers/oligomers” means that at least one kind of levulinic aciddimer/oligomer is contained.

The levulinic acid dimer/oligomer further includes all compoundsdirectly obtainable from a levulinic acid dimer/oligomer by otherreactions under the conditions of a C—C-coupling reaction ordistillation, such as (internal) lactonisation and dehydation andfurther condensation reactions producing e.g. LA-trimers. Examples oflevulinic acid dimers/oligomers according to the invention are shown bythe following formulas, using free acid dimers as examples:

In the present invention, the freezing point of the renewable middledistillate composition is preferably −70° C. or lower. Furthers thefreezing point of the renewable middle distillate composition may be−80° C. or lower, −90° C. or lower, or −95° C. or lower. The freezingpoint may be determined e.g. in accordance with IP529. The inventors ofthe present invention surprisingly found that a middle distillatecomposition obtained form levulinic add dimers/oligomers provides anextremely low freezing point, which makes it particularly suitable as anaviation fuel component or as a winter diesel component.

In the present invention, the “middle distillate composition” generallyrelates to the middle distillate fraction contained in the fuel of thepresent invention, to the middle distillate fraction produced by theprocess of the present invention and to the middle distillate fractionused in accordance with the present invention. Further, the middledistillate fraction may be a diesel range fraction or an aviation fuelrange fraction, and is preferably an aviation fuel range fraction.

Preferably the renewable middle distillate composition contains at least50 wt.-%, preferably at least 55 wt.%, more preferably at least 60wt.-%, or at least 65 wt.-% of cycloparaffin, as determined inaccordance with ASTM D2425.

High a content of cycloparaffins surprisingly provides good fuelproperties (such as low freezing point and low cloud point) and can beachieved when using levulinic acid dimers/oligomers as a feedstockmaterial by appropriately adjusting the HDO conditions.

The renewable middle distillate composition suitably contains at most 80wt-%, preferably at most 75 wt.-%, more preferably at most 72 wt.-%, orat most 70 wt.-% of cycloparaffins, as determined in accordance withASTM D2425. In general, paraffin hydrocarbons offer the most desirablecombustion cleanliness characteristics for jet fuels and diesel fuels.Cycloparaffins are the next most desirable hydrocarbons for this use.

Although the content of the middle distillate fraction in the fuel ofthe present invention is not particularly limited and may be in therange of 0.01 wt.-% to 100 wt.-% (neat middle distillate fraction), inview of adjusting the fuel properties (such as density, lubricity,viscosity, freezing point, and so on) to desired values (and or to meetregulatory requirements), it can be desirable to blend the middledistillate fraction with fossil fuel and/or with other renewable fuel(other than renewable fuel derived from HDO of a feedstock containinglevulinic acid dimers/oligomers).

Particularly, the fuel may further contain fossil fuel, HEFA(hydroprocessed ester and fatty acids) fuel and/or HVO (hydrotreatedvegetable oil) fuel.

The BOCLE lubricity of the renewable middle distillate composition maybe 0.75 mm or less, preferably 0.72 mm or less, more preferably 0.70 mmor less, 0.69 mm or less, 0.68 mm or less, or 0.67 mm or less, asdetermined in accordance with ASTM D5001-10 (2014). One of thesurprising findings of the present inventors is that the BOCLE lubricityof the middle distillate fraction, particularly of the aviation fuelfraction (LBAF; levulinic acid based aviation fuel fraction), is highlyfavourable, i.e. the middle distillate fraction achieves very low wearvalues.

Furthermore, a blend of LBAF and fossil aviation fuel can achieve evenlower BOCLE values, in particular for blends containing 1.5 wt.-% LBAFor more, preferably 2.5 wt.-% LBAF or more, 3.0 wt.-% LBAF of more, or4.0 wt.-%. LBAF or more. The effect is well pronounced even if thecontent of LBAF in the blend is 40.0 wt.-% or less, preferably 30.0 wt.%or less, 20.0 wt.-% or less, 15.0 wt.-% or less, 12.0 wt.-% or less or10.0 wt.-% or less. Preferably, the BOCLE lubricity of the fuel of thepresent invention is 0.70 mm or less, preferably 0.67 mm or less, morepreferably 0.66 mm or less, 0.65 mm or less, or 0.64 mm or less, asdetermined in accordance with ASTM D5001-10 (2014). Lubricity is a veryimportant property in diesel fuels but also in military jet fuel use.

The present invention thus suitably provides an aviation fuel componenthaving highly favourable BOCLE lubricity while at the same time allowingdesirable swelling of seal/gasket elastomers and cleaner combustion dueto low aromatics content.

Next, a method or producing a middle distillate fraction is described.The middle distillate fraction contained in the fuel of the presentinvention is preferably produced by the method of the present invention.Further, the middle distillate fraction produced by the methodpreferably has the properties of the middle distillate fraction, asdefined above for the middle distillate fraction contained in the fuelof the present invention.

The method for production of a renewable middle distillate compositioncomprises the steps of subjecting a feedstock comprising levulinic aciddimers/oligomers to at least one hydrodeoxygenation (HDO) reaction (HDOstep), and fractionating (e.g. fractionated distillation) the resultingHDO product to obtain the middle distillate composition (fractionationstep).

By employing levulinic acid dimers/oligomers the middle distillatecomposition of the present invention is particularly suited as aviationand/or diesel fuel component. That is, the composition contains high anamount of paraffinic hydrocarbons (having high a content ofcycloparaffins and isoparaffins) having 8 to 15 carbon atoms, whereinthe majority (50 by weight or more) of the product has 9 or 10 carbonatoms.

Specifically, the method of the present invention provides productshaving a high content (usually more than 50%) of paraffinic hydrocarbonsderived from levulinic acid dimers/oligomers, i.e. having 8 to 10 carbonatoms. Here, 10 is the total number of two levulinic acid carbon chainsand the reduction by 1 to 2 carbon atoms takes account of carbon loss(e.g. decarboxylation) reactions occurring in a C—C-coupling step or inthe HDO step. In this respect, a certain amount of higher molecularweight compounds (namely hydrocarbons derived from levulinic acidtrimers) can be favourable in particular for fuel applications, sincesuch a carbon number distribution mimics that of fossil oil fractions(fossil fuel).

Preferably, the middle distillate of the present invention has a boilingpoint range of 150° C. to 370° C., more preferably 150° C. to 285° C.,155° C. to 260° C., or 180° C. to 285° C. The range below 285° C. isgenerally suitable as aviation fuel, which is preferred in the presentinvention, wherein the fraction boiling in the range of 155° C. to 260°C. is particularly preferable.

The levulinic add dimers/oligomers may be obtained bydimerization/oligomerization of levulinic acid. Therefore, the method ofthe present invention may comprise a step of subjecting a raw materialcomprising at least levulinic add to a C—C coupling reaction so as toproduce the levulinic acid dimers/oligomers (C—C-coupling step). As saidabove, the levulinic acid may be in any form, such as free acid form,ester form or lactone form.

The C—C-coupling reaction may be conducted at a temperature in the rangeof 100-200° C., preferably 120-180° C., more preferably 120-160° C.,most preferably 120-140° C., especially when the C—C coupling reactionis carried out in the presence of hydrogen and using an acidic ionexchange resin (IER). This temperature range was found to beparticularly suitable for obtaining a high yield of levulinic adddimers/oligomers which are suitable to be used in the feedstock.

It is to be noted that the upper limits and the lower limits of eachrange mentioned in the present description or claims may be combined togive new ranges which are intended to be comprised in the disclosure ofthe present invention.

In an embodiment, the present invention provides a method of producingthe middle distillate fraction starting from levulinic acid. The methodcomprises the steps of providing a raw material comprising at leastlevulinic acid (preparation step), subjecting the raw material to a C—Ccoupling reaction so as to produce a C—C-coupling product containinglevulinic add dimers/oligomers (the above-mentioned C—C-coupling step),wherein the C—C coupling reaction is carried out in the presence ofhydrogen and using an acidic ion exchange resin (IER) carrying ahydrogenating metal as a catalyst, subjecting a feedstock comprising atleast the levulinic acid dimers/oligomers to a hydrodeoxygenationreaction to produce a HDO product (the above-mentioned HDO step), andfractionating the HDO product to obtain the middle distillatecomposition (the above-mentioned fractionation step).

This method is particularly preferable because it ensures that high anamount of levulinic acid dimers is produced in the C—C-coupling step inaddition to a favourable amount of trimers and higher oligomers, so thatthe HDO step can be carried out without further purification/separationor with only minor purification/separation (such as removal of levulinicacid monomer, gaseous reaction products and/or water). However, theinvention is not limited to this method and any method for producing thelevulinic acid dimers/oligomers can be applied or the levulinic aciddimers/oligomers may be purchased. As the case may be,purification/separation of the levulinic acid dimers/oligomers (e.g.fractionation) may be desirable to achieve favourable contents oflevulinic acid dimers/oligomers n the feedstock.

In the step of subjecting the feedstock to the C—C-coupling reaction,the levulinic acid undergoes a C—C-coupling reaction with anotherlevulinic acid present in the feedstock so as to produce a levulinicacid dimer/oligomer.

Depending on the actual reaction conditions, the levulinic acid mayundergo different C—C-coupling reactions. In particular the C—C-couplingreactions may be ketonisation reactions or reactions proceeding throughan enol or enolate intermediate. Accordingly, the C—C-coupling reactionsmay be aldol-type reactions and condensations, ketonisations, reactionswhere the C—C-coupling involves an alkene, as well as otherdimerization/oligomerization reactions. Further, decarboxylation,dehydration and/or hydrogenation may occur during or after theC—C-coupling reaction, thus providing a dimer/oligomer derivative havingless oxygen and/or carbon atoms than expected from the C—C-couplingreaction alone.

Without wanting to be bound to theory, it is considered that an acidicIER (ion exchange resin) catalyst catalyses mainly aldol condensationreactions of levulinic acid. Under the reaction conditions of theC—C-coupling reaction, the resulting dimers/oligomers easily undergolactonisation.

The hydrodeoxygenation (HDO) reaction may be carried out at anytemperature, preferably at a temperature of at least 200° C., at least250° C., at least 270° C., at least 290° C., at least 300° C., at least305° C., or at least 310° C. A temperature of 280° C. or more in the HDOstep leads to further (thermal) C—C-coupling reactions (furtheroligomerization reactions) in the HDO step.

Unless explicitly stated, the pressure values in the present inventionrelate to absolute pressures. Further, when, speaking of hydrogenpressure or pressure of a specific gas in general, the partial pressureof hydrogen (or the specific gas) is meant.

Furthermore,levulinic acid dimers/oligomers in the feedstock may containa keto group, an aldehyde group, an acid group (free acid form, esterform or lactone form) and/or a hydroxyl group.

In the present invention, it to be noted that the term “feedstock”includes all non-gaseous material fed to the reactor, except for thematerial, constituting the catalyst system. Thus, the calculation of thelevulinic acid dimer/oligomer content in the feedstock does not considerthe amount of catalyst. The same applies to the amounts of reactants fedin the HDO step or any other step of the methods of the presentinvention.

The method of the present invention may further comprise a step ofremoving unreacted levulinic add and other monomers (separation step)before carrying out the HDO reaction.

Under practical reaction conditions, a dimerization/oligomerizationreaction using an acidic IER catalyst system reaches a turnover oflevulinic acid of about 50% by weight. Thus about 50% by weight of theC—C-coupling reaction product consist of unreacted levulinic add(monomer). This monomer is preferably removed before the HDO step. Mostsuitably, the monomer is removed immediately after the C—C-couplingreaction. Distillation is a suitable method for removing the monomer,but other methods may be employed as well. Specifically, theC—C-coupling reaction product may be fractionated to remove potentialunreacted levulinic acid monomers and other light components such aswater and CO₂ formed in the C—C-coupling. The unreacted levulinic add(monomer) may be recycled and combined with the raw material.

The hydrogenation hydrodeoxygenation reactions during levulinic acidcondensation step may be carried out using a hydrogenating metal as acatalyst, wherein the hydrogenating metal is selected from metals of theGroup VIII of the Periodic Table of Elements, preferably Co, Ni, Ru, Rh,Pd, and Pt, more preferably Pd, or a combination thereof.

These metals, in particular Pd, has been found to provide goodhydrogenation properties and being well compatible with the requirementsof the C—C-coupling reaction using, an IER.

The present invention further relates to a use of a renewable middledistillate composition obtainable by hydrodeoxygenation of levulinicacid dimers/oligomers, followed by fractionated distillation, as anaviation fuel or aviation fuel component. When used as aviation fuel,the middle distillate fraction is prepared as an aviation fuel fraction,having a boiling point range in the aviation fuel range. The renewablemiddle distillate composition can be used as a diesel fuel or dieselfuel component as well, in particular as a winter diesel fuel component.

Preferably, the renewable middle, distillate composition in accordancewith the above-mentioned use is obtainable by the method of the presentinvention and/or has the properties as recited for the middle distillatefraction contained in the fuel of the present invention. In other words,it is preferable that the middle distillate compositions of the fuel,the method and the use; of the present invention are the same.

Further aspects of the present invention are described in the following,while all of these aspects can be combined with the above-mentionedaspects without limitation.

In the method step employing hydrogen, the hydrogen may be mixed withone or more other gases (dilution gas), preferably an inert gas such asnitrogen, argon, helium or another of the noble gases, or gas behavinginertly to the reaction conditions of the present invention. By behavinginertly it is meant that the gas should not to a major extentparticipate as a reaction member, and preferably the inert gas shouldparticipate as little as possible, such as not participate at all.

While high a hydrogen pressure in the C-coupling step requires moresophisticated equipment, it is nevertheless possible to omit the mildhydrogenation step without needing to use, long reaction times or highlyreactive catalysts. Furthermore, a high hydrogen pressure in theC—C-coupling step was surprisingly found to shift the C—C-couplingreaction product (dimer/oligomer) from the lactone form to the diacidform. Since the lactone form dimers/oligomers tend to result innaphthenic or aromatic products after HDO, this embodiment isparticularly suitable for the production of gasoline, Jet fuelcomponents and chemical components.

The hydrogen pressure in this embodiment of the C—C-coupling step ispreferably at least 35 bar, more preferably at least 40 bar, furtherpreferably in the range of 45 to 55 bar. However, the upper hydrogenpressure is not necessarily limited and may be 200 bar or less, 100 baror less, 80 bar or less, 70 bar or less, or 60 bar or less.

The C—C-coupling reaction can be controlled by adjusting severalparameters, including by selection of reaction conditions such as weighthourly space velocity (WHSV) (kg feedstock/kg catalyst per hour).

The raw material may be obtained from processing of lignocellulosicmaterial, and such processed material may be used directly, or purifiedto varying degrees before being used as a raw material in the method ofthe present invention. The levulinic acid may be produced e,g. with theBiofine method disclosed in U.S. Pat. No. 5,608,105.

Preferably, in the hydrodeoxygenation step, a HDO catalyst is employedwhich comprises a metal having hydrogenation catalyst function on asupport, such as for example a HDO catalyst metal selected from a groupconsisting of Pd, Pt, Ni, Co, Mo, Ru, Rh, W or any combination of these.The metal having hydrogenation catalyst function may be carried on asupport, preferably an inorganic oxide support, more preferably silica,alumina, titanic, zirconia, carbon or a combination thereof. A highlypreferable HDO catalyst comprises sulfided NiMo, which is preferablysupported on an inorganic oxide such as alumina.

The hydrodeoxygenation step may be conducted at a temperature of up to500° C. and at a pressure of 10-150 bar.

The method of the present invention may be carried out in a reactor,such as a stirred tank reactor, preferably a continuous stirred tankreactor, or a tubular flow reactor, preferably a continuous flowreactor. Further, the individual steps of the present invention may becarried out in the same reactor or in different reactors. Preferably,the C—C-coupling step and the HDO step are carried out in differentreactors.

The product of the HDO step may optionally be subjected to anisomerization step in the presence of hydrogen and an isomerizationcatalyst. Both the HDO step and isomerisation step may be conducted inthe same reactor. In some embodiments, the isomerisation catalyst is anoble metal bifunctional catalyst, for example Pt-SAPO orPt-ZSM-catalyst. The isomerization step may for example be conducted ata temperature of 200-400° C. and at a pressure of 20-150 bar.Fractionation may be carried out before or after isomerization, but ispreferably carried out after isomerization. Preferably, no isomerizationtreatment is carried out.

EXAPLES Example 1 Production of Levulinic Acid Dimer

A raw material containing 98 wt.-parts commercial grade levulinic acid(97 wt-% purity) and 2 wt.-parts water was provided. The raw materialand hydrogen were fed to a tubular reactor supporting Amberlyst CH-34catalyst (trade name; Pd doped ion exchange resin). The temperature inthe reactor was adjusted to 130° C., the hydrogen pressure was 20 bar,WHSV was 0.2 h⁻¹ and hydrogen to raw material (liquid raw material) flowratio was 1170 NI/I.

The C—C-coupling product obtained after the tubular reactor contained 44wt.-% non-reacted levulinic acid (LA) and γ-valerolactone (GVL), 53wt.-% dimers and about 2 wt.-% oligomers. The non-reacted LA (+GVL) aswell as light reaction products (e.g. CO₂) and water were separated bydistillation.

The distilled product (C—C-coupling) had a LA dimer content of 95 wt.-%.

Example 2 HDO of LA Dimer/Oligomer

The product of Example 1 was subjected to HDO in a tubular reactor at ahydrogen pressure of 80 bar, a temperature of 306° C., and WHSV of 0.3h⁻¹, using a sulfided NiMo hydrogenation catalyst supported on aluminaand a flow rate of hydrogen to C—C-coupling of 2100 NI/I.

The HDO product was fractionated and the composition of the thusobtained LBAF fraction (levulinic acid based aviation fuel fraction)(155-260° C.) was evaluated. The results are shown in Table 1, whichfurther shows typical properties of fossil Jet A-1 fuel (by Neste), andHEFA component Jet fuel requirements (ASTM D7566 specification) andconventional Jet A1 requirements. The latter covers also Jet A1 fuelcontaining synthesized hydrocarbons (i.e. HEFA component).

The viscosity of the fuel is closely related to the pumpability over thetemperature range and consistency of nozzle spray patterns. The main Jetfuel specifications allow a maximum viscosity (at −20° C.) of 8 mm²/s. Amaximum viscosity value of 12 mm²/s at −40° C. is an operating limitprovided by some of the aviation OEM's.

As can be seen, the test results comply with JET A-1 requirements, whilethe lubricity is even better than that of conventional fossil fuel.However, any new production route and component will anyways requireASTM certification.

Example 3 Blends of LBAF and Fossil Fuel

LBAF was prepared in the same manner as in Example 2, Blends of fossilJet A-1 fuel (by Neste) and LBAF were tested for their freezing pointsand BOCLE lubricity. The results are shown in Table 2 and FIG. 1.

Example 4 Blends of LBAF and NEXBTL Fuel

LBAF was prepared in, the same manner as in Example 2, except for usingan aviation fuel fraction having a boiling point range of 180-285° C.Blends of NEXBTL jet fuel 1 (HEFA-SPK Jet A-1 fuel by Neste; produced inaccordance with Example 1 of EP 2141217 B1) and LBAF were tested and theresults are shown in Table 3.

Reference Example 5 Levulinic Acid Based Diesel

LA based diesel was prepared in the same manner as in Example 2, exceptfor using a diesel fuel fraction having a boiling point range of180-360° C. Test results are shown in Table 4.

TABLE 1 Neste ASTM Fossil D7566 JET A-1 A2 (HEFA JET A-1 (typicalAnalysis Test method LBAF (Ex. 2) component) requirement values)Density, kg/m³ ASTM D4052     785.4 730-770 775-840 789.9 viscosity −20°C., ASTM D445      2.849 — max 8 2.828 mm²/s viscosity −40° C., ASTMD445      5.056 — — — mm²/s Freezing point, ° C. IP 529  <−80 *) max −40max −47 −68.7 distillation ° C.: ASTM D86 10 vol-%     164.9 max 205 max205 163.6 FBP     247.2 max 300 max 300 233.3 residue, vol-%      1.3max 1.5 max 1.5 1.3 loss vol-%      0.6 max 1.5 max 1.5 0.6 Existentgum, IP 540      5 max 7 max 7 1 mg/100 ml BOCLE lubricity. ASTM D5001     0.67 — max 0.85 0.79 mm HFRR lubricity ENISO12156-1     679 — — —μm/60° C. Paraffins, wt.-%      30.0 reported ASTM D2425 Cycloparaffins/     67.4 max 15 naphthenes wt.-% ASTM D2425 Aromatics, wt.-%      2.6max 0.5 ASTM D2425 Olefins, wt.-%    <0.1 ASTM D2425 *) Crystal notdetected till −100° C.

TABLE 2 LBAF Ex. 3 BOCLE (rest in fossil) (mm) 100 wt.-% 0.67  70 wt.-%—  50 wt.-% 0.67  30 wt.-% 0.65  15 wt.-% —  10 wt.-% 0.64  5 wt.-% 0.63 1 wt.-% 0.69  0 wt.-% 0.71

TABLE 3 80% NEXBTL NEXBTL LBAF jet Property Method jet (Ex 3) 20% LBAFTotal aromatics, wt-% EN12916, <0.5 7.6 1.52 ASTM D2425 (calculated)Monoaromatics, wt-% EN12916 N/A 7.6 Di-aromatics, wt-% EN12916 N/A <0.1Tri+aromatics, wt-% EN12916 N/A <0.1 Naphthenes, wt-% ASTM D2425 0.8861.1 12.92 (calculated) Density, kg/m3 ENISO12185, 769.3 N/A 781.6 ASTMD4052 Freezing point, ° C. IP529 −51.8 N/A −54.1 Distillation ASTMD7345, N/A ASTM D86 IBP N/A N/A 155.1 10% (T10) 185.8 N/A 185.4 50%(T50) 260.1 N/A 253.7 90% (T90) 281.4 N/A 282.7 FBP 289.2 N/A 300.0residue 1.3 N/A 1.5 loss 1.2 N/A 0.5 T90-T10 95.6 N/A 97.3

TABLE 4 Ex. 5 COMPOSITION Aromatics 11.8 wt-% PROPERTIES Cetane Number47 Density 15° C. 854 kg/m³ Cloud point <−95° C. Viscosity 40° C. 3.6mm²/s Gross heating value 45.9 MJ/kg HFRR 496 μm (micro-m) TAN <0.1 mgKOH/g

1. A fuel comprising: a renewable middle distillate composition, whereinthe renewable middle distillate composition is obtained from a feedstockhaving dimers and/or oligomers of levulinic acid and/or of levulinicacid derivatives (levulinic acid dimers/oligomers), subjected tohydrodeoxygenation followed by fractionated distillation, wherein therenewable middle distillate composition contains less than 10.0 wt.-%aromatics, as determined in accordance with ASTM D2425.
 2. The fuelaccording to claim 1, wherein the renewable middle distillatecomposition contains at most 9.5 wt.% of aromatics, as determined inaccordance with ASTM D2425.
 3. The fuel according to claim 1, whereinthe freezing point of the renewable middle distillate composition is−70° C. or lower.
 4. The fuel according to claim 1, wherein therenewable middle distillate composition contains at least 50 wt. % ofcycloparaffins, as determined in accordance with ASTM D2425.
 5. The fuelaccording to claim 1, wherein the renewable middle distillatecomposition contains at most 80 wt.% of cycloparaffins, as determined inaccordance with ASTM D2425.
 6. The fuel according to claim 1, whereinthe fuel further contains fossil fuel, HEFA (hydroprocessed ester andfatty acids) fuel and/or HVO (hydrotreated vegetable oil) fuel.
 7. Thefuel according to claim 1, wherein the BOCLE lubricity of the renewablemiddle distillate composition is 0.75 mm or less as determined inaccordance with ASTM D5001-10 (2014).
 8. A method for production of arenewable middle distillate composition, the method comprising:subjecting a feedstock containing dimers and/or oligomers of levulinicacid and/or of levulinic acid derivatives (levulinic aciddimers/oligomers) to at least one hydrodeoxygenation (HDO) reaction; andfractionating the a resulting HDO product to obtain the middledistillate composition, wherein the renewable middle distillatecomposition contains less than 10.0 wt.-% aromatics, as determined inaccordance with ASTM D2425.
 9. The method according to claim 8, whereinthe renewable middle distillate composition contains at most 9.5wt.% ofaromatics, as determined in accordance with ASTM D2425.
 10. The methodaccording to claim 8, comprising: subjecting a raw material containingat least levulinic acid to a C—C coupling reaction so as to produce thedimers and/or oligomers of levulinic acid and/or of levulinic acidderivatives (levulinic acid dimers/oligomers).
 11. The method accordingto claim 10, wherein the C—C-coupling reaction is conducted at atemperature in the range of 100-200° C.
 12. The method according toclaim 8, comprising: providing a raw material containing at leastlevulinic acid and/or a derivative thereof; subjecting the raw materialto a C—C coupling reaction, wherein the C—C coupling reaction is carriedout in a presence of hydrogen and using an acidic ion exchange resincarrying a hydrogenating metal as a catalyst, so as to produce aC—C-coupling containing dimers and/or oligomers of levulinic acid and/orof levulinic acid derivatives (levulinic acid dimers/oligomers);subjecting a feedstock containing at least the levulinic aciddimers/oligomers to a hydrodeoxygenation (HDO) reaction to produce a HDOproduct; and fractionating the HDO product to obtain the middledistillate composition.
 13. A method for producing a fuel having arenewable middle distillate composition, wherein the renewable middledistillate composition is obtained from a feedstock having dimers and/oroligomers of levulinic acid and/or of levulinic acid derivatives(levulinic acid dimers/oligomers), subjected to hydrodeoxygenationfollowed by fractionated distillation, wherein the renewable middledistillate composition contains less than 10.0 wt.-% aromatics, asdetermined in accordance with ASTM D2425, wherein the middle distillatecomposition is obtained by a method comprising: subjecting the feedstockcontaining dimers and/or oligomers of levulinic acid and/or of levulinicacid derivatives (levulinic acid dimers/oligomers) to at least onehydrodeoxygenation (HDO) reaction; and fractionating a resulting HDOproduct to obtain the middle distillate composition, wherein therenewable middle distillate composition contains less than 10.0 wt.-%aromatics, as determined in accordance with ASTM D2425.
 14. The fuelaccording to claim 1, wherein the renewable middle distillatecomposition obtained by hydrodeoxygenation of dimers and/or oligomers oflevulinic acid and/or of levulinic acid derivatives (levulinic aciddimers/oligomers), followed by fractionated distillation, is an aviationfuel or aviation fuel component.
 15. The fuel according to claim 1,wherein the renewable middle distillate composition contains at most 3.0wt.-% of aromatics, as determined in accordance with ASTM D2425.
 16. Thefuel according to claim 2, wherein the freezing point of the renewablemiddle distillate composition is −95° C. or lower.
 17. The fuelaccording to claim 2, wherein the renewable middle distillatecomposition contains at least 55 wt.-% of cycloparaffins, as determinedin accordance with ASTM D2425.
 18. The fuel according to claim 2,wherein the renewable middle distillate composition contains at most 70wt.-% of cycloparaffins, as determined in accordance with ASTM D2425.19. The fuel according to claim 2, wherein the BOCLE lubricity of therenewable middle distillate composition is 0.67 mm or less, asdetermined in accordance with ASTM D5001-10 (2014).
 20. The methodaccording to claim 8, wherein the renewable middle distillatecomposition contains at most 3.0 wt.-% of aromatics, as determined inaccordance with ASTM D2425.
 21. The method according to claim 20,comprising: subjecting a raw material containing at least levulinic acidto a C—C coupling reaction so as to produce the dimers and/or oligomersof levulinic acid and/or of levulinic acid derivatives (levulinic aciddimers/oligomers).
 22. The method according to claim 10, wherein theC—C-coupling reaction is conducted at a temperature in the range of120-140° C.